JP3086002B2 - Polyurethane composition or polyurethane-urea composition and coated roll using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyurethane composition having excellent water resistance, chemical resistance, heat resistance, weather resistance and the like.
It relates to a coating roll coated on the surface,
It can be effectively used as a roll for steel, paper, and office equipment .

[0002]

2. Description of the Related Art Conventionally, thermosetting polyurethane elastomers have a wide selection of hardness and elasticity, and have excellent flexing and abrasion resistance, including excellent shock absorbing power. Rolls, belts, solid tires, sheets, plate materials, round bars, square bars, pipes, square materials, etc. for steel, paper, and office equipment because of their excellent oil resistance and high tear strength. Used in

The thermosetting polyurethane elastomer is a prepolymer obtained by reacting polyoxypropylene glycol (PPG), polyoxytetramethylene glycol (PTMG), polyester polyol, or the like with an excess of polyisocyanate. It is used after being cured using a polyamine such as (2-chloroaniline) or a polyol.

Among the polyols described above, those having the best physical properties are those using PTMG-based prepolymers. However, with the advancement of technology in recent years, stricter water resistance, moisture resistance and chemical resistance are required. In addition, excellent raw materials are required.

The inventors of the present invention have tried to apply a butadiene oligomer containing a hydroxyl group, since it is known as a raw material for obtaining a polyurethane having excellent water resistance and chemical resistance. It was found that although the chemical resistance was improved, there was a major drawback that the heat resistance and weather resistance were not good.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of intensive studies to solve such problems, a specific polyol compound or a polyamine is added to a prepolymer obtained by reacting a hydride of a liquid isoprene-based polymer containing a specific hydroxyl group with a polyisocyanate compound. The present inventors have found that a polyurethane-based composition containing a compound solves the above-mentioned conventional problems, and based on this finding, have completed the present invention.

That is, the present invention relates to a hydride (a) of a hydroxyl group-containing liquid isoprene polymer having an average number of hydroxyl groups per molecule of 2.0 or more and a polyisocyanate compound (b)
And a molecular weight of 500
Coating a metal surface with a polyurethane composition or a polyurethane-urea composition comprising at least one compound selected from the following polyol compounds and polyamine compounds:
The present invention is to provide a coating roll comprising:

In the present invention, as the component (a), 1
A hydride of a hydroxyl group-containing liquid isoprene-based polymer having an average number of hydroxyl groups per molecule of 2.0 or more is used. The hydride of the hydroxyl-containing liquid isoprene-based polymer can be obtained by hydrogenating the hydroxyl-containing liquid isoprene-based polymer using a known method.

The hydroxyl group-containing liquid isoprene-based polymer has a number average molecular weight of usually 300 to 25,000, preferably 500 to 10,000, and a hydroxyl group content of 0.1 to 0.1.
It is 10 meq / g, preferably 0.3 to 7 meq / g. Also,
Structurally, cis-1,4 structure and trans-1,4 structure
It is preferred that the total structure accounts for 70% or more. The hydroxyl group may be located at the end of the molecular chain or at the end of the molecular chain, but is preferably located at the end of the molecular chain. Further, two or more types of hydroxyl group-containing liquid isoprene-based polymers may be used.

[0010] Such a hydroxyl group-containing liquid isoprene-based polymer can be easily produced by a known method. Specifically, for example, an isoprene monomer is converted to hydrogen peroxide, an azo compound having a hydroxyl group (for example, 2,2′-
Azobis [2-methyl-N- (2-hydroxyethyl)
-Propionamide] or a peroxide having a hydroxyl group (for example, cyclohexanone peroxide or the like) as a polymerization initiator to obtain a hydroxyl group-containing liquid polyisoprene by radical polymerization.

The amount of the polymerization initiator used at this time is, for example, 1.0 to 1.0 g of hydrogen peroxide per 100 g of diene monomer.
50 g is appropriate and 2,2'-azobis [2-methyl-N- (2-hydroxyeral) -propionamide]
Or 5.0-100 g of cyclohexanone peroxide
Is appropriate. As the polymerization initiator, it is preferable to use hydrogen peroxide. The polymerization can be carried out without a solvent, but it is preferable to use a solvent because the reaction can be easily controlled. As the solvent, ethanol,
Isopropanol, n-butanol and the like are usually used. The reaction temperature is 80 to 150 ° C, and the reaction time is 0.5 to 15
Time is appropriate.

Further, at the time of polymerization, an addition-polymerizable monomer having 2 to 22 carbon atoms (butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid) in a proportion of 50 mol% or less based on the isoprene monomer. Acid and its ester, vinyl chloride,
Vinyl acetate, acrylamide, etc.) and diene monomers having 4 to 22 carbon atoms (butadiene, chloroprene, 1,3-
Pentadiene, cyclopentadiene, etc.) can also be added.

After completion of the reaction, the solvent is removed by distilling the solution under reduced pressure to obtain a hydroxyl group-containing liquid isoprene-based polymer.

In the present invention, a hydride of a hydroxyl group-containing liquid isoprene polymer obtained by further hydrogenating the thus obtained hydroxyl group-containing liquid isoprene polymer is used as the component (a). . The hydride of such a hydroxyl group-containing liquid isoprene-based polymer is obtained by a known method using a homogeneous catalyst, a heterogeneous catalyst, or the like.
It can be obtained by hydrogenating the hydroxyl group-containing liquid isoprene-based polymer produced as described above.

First, when a homogeneous catalyst is used, hexane,
Saturated hydrocarbons such as cyclohexene and aromatic hydrocarbons such as benzene, toluene and xylene are used as solvents,
At a reaction temperature of 50 ° C., the hydrogenation reaction is carried out under a hydrogen pressure of normal pressure to 50 kg / cm ² . As a homogeneous catalyst, a Ziegler catalyst or the like obtained by combining a transition metal halide with an alkylated product such as aluminum, an alkaline earth metal or an alkali metal may be used in an amount of 0.
It may be used in an amount of about 01 to 0.1 mol%. The reaction is usually
It ends in 1 to 24 hours.

On the other hand, when a heterogeneous catalyst or the like is used, saturated hydrocarbons such as hexane and cyclohexene; ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; alcohols such as ethanol and isopropanol; Using the system as a solvent, room temperature to 2
At a reaction temperature of 00 ° C., the hydrogenation reaction is carried out under a hydrogen pressure of normal pressure to 100 kg / cm ² . As the heterogeneous catalyst, a catalyst such as nickel, cobalt, palladium, platinum, rhodium, ruthenium or the like may be used alone or supported on a carrier such as silica, diatomaceous earth, alumina and activated carbon. The amount of the catalyst used is 0.05 to 10 based on the weight of the polymer.
wt% is appropriate. These catalysts may be used as a mixture of two or more kinds. The reaction is usually completed in 1 to 48 hours.

After completion of the reaction, the catalyst is filtered off and the solution is distilled under reduced pressure to remove the solvent and obtain a hydride of a hydroxyl group-containing liquid isoprene-based polymer.

The hydride of the hydroxyl group-containing liquid isoprene polymer thus obtained has a number average molecular weight of 300.
~ 25000, preferably 500-10000,
Those having a hydroxyl group content of 0.1 to 10 meq / g are desirable.

In the present invention, it is necessary to use a hydride of a hydroxyl group-containing liquid isoprene polymer having an average number of hydroxyl groups per molecule of 2.0 or more. When the average number of hydroxyl groups is less than 2.0, not only the water resistance and chemical resistance of the obtained composition are lowered, but also the heat aging resistance,
It is not preferable because the weather resistance is remarkably inferior. 1
The average number of hydroxyl groups per molecule is represented by the following equation.

[0020]

(Equation 1)

The hydrogenation rate of the hydride of the hydroxyl group-containing liquid isoprene polymer is preferably at least 50%, particularly preferably at least 70%. Furthermore, a mixture of two or more hydrides of a hydroxyl group-containing liquid isoprene-based polymer can also be used. The hydrogenation rate, that is, the rate of hydrogenation of the unsaturated double bond in the polymer after the hydrogenation reaction is represented by the following formula.

[0022]

(Equation 2)

Next, in the present invention, a polyisocyanate compound is used as the component (b). This polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has a reactive isocyanate group to a hydroxyl group of a hydride of the above-mentioned hydroxyl-containing liquid isoprene-based polymer.

As the polyisocyanate compound,
The usual aromatic, aliphatic and alicyclic ones can be mentioned. Specifically, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MD
I), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, isopropylbenzene-2,4 -Aromatic polyisocyanates such as diisocyanate.

Further, xylylene diisocyanate (XD
I), tetramethylxylylene diisocyanate (TM
XDI) or other aliphatic-aromatic polyisocyanate (a polyisocyanate in which an isocyanate group is bonded to an aromatic ring via an aliphatic hydrocarbon, that is, a polyisocyanate having no isocyanate group directly bonded to an aromatic ring in the molecule). Isocyanates). Next, hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate,
Examples thereof include aliphatic polyisocyanates such as 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylene triisocyanate, and trimethylhexamethylene diisocyanate.

Further, transcyclohexane-1,4
-Alicyclic polyisocyanates such as diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and the like. .

In addition, cyclized trimers (modified isocyanurates) and burettes of the above polyisocyanate compounds, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol,
Trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol,
Addition products of polyol compounds such as polyalkadiene polyols, hydrides of polyalkadiene polyols, partially saponified ethylene-vinyl acetate copolymers, castor oil-based polyols, and the above-mentioned polyisocyanate compounds can be used.

Further, these polyisocyanate compounds may be used as a mixture of two or more kinds.
Use a so-called blocked isocyanate compound blocked with a blocking agent such as phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite, and boric acid. You can also.

The prepolymer used in the present invention is obtained by reacting the above-mentioned hydride of a hydroxyl group-containing liquid isoprene-based polymer (a) with a polyisocyanate compound (b). Is obtained by reacting the components (a) and (b) at a temperature of 0 to 150 ° C., preferably 20 to 120 ° C., for 0.1 to 100 hours, preferably 0.5 to 50 hours. Can be. At this time, the molar ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate compound (b) to the hydroxyl group (OH) of the hydride (a) of the hydroxyl group-containing liquid isoprene-based polymer is usually 1.7 to 5.0.

In obtaining the prepolymer,
Various additives as described below can be added at any suitable time before, during or after the reaction. At this time, when a compound having a hydroxyl group or an amino group that reacts with an isocyanate group, such as a polyol compound or a polyamine compound, is added as an additive, the hydroxyl group of all the compound having a hydroxyl group (including hydride) to be added is added. (OH), the molar ratio of isocyanate groups to amino groups (NH ₂ ) of the compound having all amino groups (NCO /
OH, NCO / NH ₂ or NCO / (OH + NH ₂ ) is blended so as to finally have the above ratio.

That is, in the present invention, a low molecular weight polyol, a polymerization type polyol,
Additives such as polyol compounds such as castor oil-based polyols and polyamine compounds can be added. Here, the polyol compound is a compound having two or more hydroxyl groups in one molecule, and includes a low molecular weight polyol, a polymerization type polyol, and a castor oil-based polyol as described above.

First, as the low molecular weight polyol, any of primary polyol, secondary polyol and tertiary polyol may be used. Specific examples of such low molecular weight polyols include, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2- Pentanediol, 2,3-pentanediol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N, N-bis-2-
Examples include low molecular weight polyols containing a hydrogen group bonded to at least one secondary carbon such as hydroxypropylarline, N, N'-bishydroxyisopropyl-2-methylpiperazine, and propylene oxide adduct of bisphenol A. it can.

Further, as the polyol, ethylene glycol not containing a hydroxyl group bonded to a secondary carbon, diethylene glycol, 1,3-propylene glycol, 1,1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can also be added. The molecular weight of these polyols is usually in the range of 50-500.

Next, as long as the gist of the present invention is not impaired,
The polymerization type polyol used as a polyurethane raw material can be added at the time of prepolymer synthesis. Specific examples of such a polymerizable polyol include, for example, polyether polyols and modified products thereof, polytetraethylene ether glycol, THF / alkylene oxide copolymerized polyols, epoxy resin-modified polyols, polyester polyols, polydiene-based polyols, and partial ketones. Polyols such as a hydrogenated ethylene-vinyl acetate copolymer can be used. The average molecular weight of these polyols is usually from 500 to 10,000.

Further, castor oil polyol can be added at the time of prepolymer synthesis. Castor oil polyols include castor oil, hydrogenated castor oil, castor oil transesterified products, and the like, and two or more of these polyols can be used as a mixture.

In the present invention, a polyamine compound is further exemplified as an additive that can be added during the synthesis of the prepolymer. Here, the polyamine compound is a compound having two or more amino groups having active hydrogen in one molecule. Specific examples of such a polyamine compound include aliphatic polyamines such as hexamethylenediamine and polyoxypropylene polyamine, and 3,3 ′.
Alicyclic polyamines such as -dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dichloro-4,
Aromatic polyamines such as 4'-diaminodiphenylmethane, 3,5-diethyltoluene-2,4-diamine, and 3,5-diethyltoluene-2,6-diamine can be given.

The above-mentioned polyol compound or polyamine compound is used in an amount of 100 parts by weight or less based on 100 parts by weight of the hydride of the above-mentioned hydroxyl group-containing liquid isoprene polymer.
Preferably, it can be added at a ratio of 50 parts by weight or less at the time of prepolymer synthesis.

Next, in the present invention, a polyurethane composition or a polyurethane-urea composition is added to the prepolymer obtained as described above by adding at least one compound selected from a polyol compound having a molecular weight of 500 or less and a polyamine compound. Get.

Here, the polyol compound is a compound having two or more hydroxyl groups in one molecule, and it is necessary to use a compound having a molecular weight of 500 or less. Has a molecular weight of 60 to 4
80 low molecular weight polyols and castor oil-based polyols. If the molecular weight is not more than 500, the object of the present invention cannot be achieved.

As the low molecular weight polyol, any of a primary polyol, a secondary polyol and a tertiary polyol may be used. Specific examples of such low molecular weight polyols include, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-
Butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2,5-
Hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N, N-bis-2-hydroxypropylalline, N, N'-bishydroxyisopropyl-2- Examples include low molecular weight polyols containing a hydrogen group bonded to at least one secondary carbon, such as methylpiperazine and a propylene oxide adduct of bisphenol A.

Further, as the polyol, ethylene glycol not containing a hydroxyl group bonded to a secondary carbon, diethylene glycol, 1,3-propylene glycol, 1,1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can also be added. The molecular weight of these polyols is 5
00 or less, usually in the range of 50 to 500.

Further, a castor oil polyol having a molecular weight of 500 or less can be used. Castor oil polyols include castor oil, hydrogenated castor oil, castor oil transesterified products, and the like, and two or more of these polyols can be used as a mixture.

Next, in the present invention, the molecular weight of 50
A polyamine compound can be used in place of the polyol compound of 0 or less. Here, the polyamine compound is
A compound having two or more active hydrogen-containing amino groups in one molecule. As such polyamine compounds, specifically, aliphatic polyamines such as hexamethylenediamine, polyoxypropylene polyamine, and 3,
Alicyclic polyamines such as 3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dichloro-
Examples thereof include aromatic polyamines such as 4,4'-diaminodiphenylmethane, 3,5-diethyltoluene-2,4-diamine, and 3,5-diethyltoluene-2,6-diamine.

In the present invention, a catalyst may be added to promote the reaction, or an inorganic filler, an organic filler, a viscosity modifier and other additives may be added according to the purpose. .

As the catalyst, for example, triethylenediamine, tetramethylguanidine, N, N, N '
N′-tetramethylhexane 1,6-diamine, N,
N, N'N "N" -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,
2-dimethylimidazole, N-methyl-N '-(2-
Tertiary amines such as dimethylamino) -ethylpiperazine and diazabicycloundecene and their carboxylate salts, stannasoctoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marcatide, dibutyltin thiocarboxylate, dibutyltin thiocarboxylate, and dibutyltin dicarboxylate Maleate, dioctyltin marker peptide, dioctyltin thiocarboxylate, phenylmercury propionate,
Organometallic compounds such as octenoates can be mentioned.

The addition amount of such a catalyst is at most 10 parts by weight based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene-based polymer. Here, when the addition amount exceeds 10 parts by weight, the effect of accelerating hardening is not only leveled off, but also the risk of local abnormal reaction (gelation) is undesirably increased.

As the inorganic filler, for example, zinc,
Asbestos, alumina, aluminum, kaolin clay, glass spheres, glass flakes, glass fiber, carbon (channel black, furnace black, acetylene black, thermal black), carbon fiber, nepheline, cryolite, graphite, silica, wollastonite, Diatomaceous earth, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, aluminum hydroxide, magnesium hydroxide, slate powder, zeolite, quartz powder, calcium carbonate, magnesium carbonate, talc, potassium titanate, boron nitride, long Stone powder, copper, nickel, molybdenum disulfide, barium sulfate, whiting, lauric clay, mica, gypsum and the like can be mentioned.

Examples of the organic filler include rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, natural fibers such as cotton, hemp, wool, silk, nylon, polyester, and the like. Vinylon, acetate,
Synthetic fibers such as acrylic, polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
Examples thereof include powders or granules of synthetic resins such as polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), epoxy, and phenol.

The compounding amount of the inorganic filler and the organic filler is 100 parts by weight or less based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene-based polymer.

As the viscosity modifier, for example, a plasticizer such as dioctyl phthalate, a paraffin-based, naphthene-based, or aroma-based process oil, an olefin oligomer, an alkylbenzene, an alkylnaphthalene, an alkyldiphenylethane, or a silicone oil may be used. Can be. The amount of the viscosity modifier is not particularly limited, but is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene-based polymer.

Further, other additives such as a solvent, a tackifying resin, an antioxidant, an antioxidant, an ultraviolet absorber, a flame retardant, an antifoaming agent and an antifoaming agent are added before, during or after the reaction. It can also be incorporated at any later time.

The solvent is added to lower the viscosity. Specifically, for example, hydrocarbon solvents such as n-hexane, cyclohexane, toluene and xylene, ketone solvents such as methyl ethyl ketone and cyclohexanone, and esters such as butyl acetate Solvent, ester solvents such as tetrahydrofuran, N, N-diethylformamide, dimethylsulfoxide and the like. The amount of the solvent is not particularly limited, but is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene-based polymer.

For adjusting the adhesive strength and the adhesive strength, a tackifying resin is used. Specifically, for example, alkylphenol resin, terpene resin, terpene phenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, cumarone resin, aliphatic and alicyclic and aromatic petroleum resins are used.

Further, in order to improve heat resistance and weather resistance, antioxidants such as hindered phenols, hindered amines, and benzotriazoles, antioxidants, ultraviolet absorbers, etc. may be added. Flame retardants such as halogen compounds and antimony oxide, defoamers such as silicone compounds, and foaming inhibitors such as zeolite and quicklime can also be blended.

The polyurethane or polyurethane-urea composition of the present invention may be composed of the prepolymer obtained as described above and at least one compound selected from a polyol compound having a molecular weight of 500 or less and a polyamine compound. Although there is no particular limitation on the preparation method, the general preparation method is shown below. For example, the composition comprises:
The prepolymer as described above and at least one compound selected from a polyol compound having a molecular weight of 500 or less and a polyamine compound are mixed at a temperature of 0 to 150 ° C. with 0.1 to 0.1.
It can be obtained by reacting for 500 minutes.

These components include a hydroxyl group (OH) of a polyol compound and / or an amino group (N
H ₂ ), isocyanate groups of the prepolymer (NC
O) molar ratio (NCO / OH, NCO / NH ₂ or N
_{CO / (OH + NH 2)} ) is blended so that 0.5 to 1.5. At this time, when the prepolymer reacts with the polyol compound, a polyurethane composition containing a urethane bond is obtained. When the prepolymer reacts with the polyamine compound, a polyurethane-urea composition containing a urea bond and a urethane bond generated during the synthesis of the prepolymer is obtained.

The composition obtained in this manner was applied to a metal surface
Obtain the target coating roll by coating the surface
be able to.

[0058]

Next, the present invention will be described in detail with reference to examples.

Preparation Example 1 (1) Preparation of Liquid Polyisoprene Having a Hydroxyl Group at the Molecular Chain Terminal 200 g of isoprene, 40 g of a 20% strength hydrogen peroxide solution and 100 g of isopropanol were charged into a 1 liter stainless steel pressure-resistant reaction vessel. The reaction was carried out at 120 ° C. and a maximum pressure of 8 kg / cm ² for 2 hours. After the reaction is over,
The reaction mixture was put into a separating funnel, 600 g of water was added thereto, and the mixture was shaken. After allowing to stand for 3 hours, the oil layer was separated. From this oil layer, the solvent, monomer and low-boiling components were removed at 2 mmHg, 10
Distillation was performed at 0 ° C. for 2 hours to obtain a liquid polyisoprene having a hydroxyl group at a molecular chain terminal (yield: 66% by weight). This had a number average molecular weight of 2,240, a hydroxyl group content of 0.96 meq / g, a viscosity of 64 poise / 30 ° C., and a bromine value of 220 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.15. In addition, the structural analysis result by ¹ H-NMR shows that the trans-1,4-structure is 57%,
33% cis-1,4 structure, 6% 1,2 structure, 3,4
The structure was 4%.

(2) Preparation of a hydride of liquid polyisoprene having a hydroxyl group at the terminal of a molecular chain 100 g of a liquid polyisoprene having a hydroxyl group at a terminal of a molecular chain obtained as described in (1) above and containing 5% by weight of ruthenium 5 g of a ruthenium carbon catalyst and 100 g of cyclohexane as a solvent were charged, and a hydrogenation reaction was carried out at 150 ° C. for 6 hours under a hydrogen pressure of 50 kg / cm ² G. After the completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter.
The solvent was distilled off under the condition of time. As a result, a hydride of liquid polyisoprene having a hydroxyl group at a molecular chain terminal was obtained. Its number average molecular weight was 2310, its hydroxyl group content was 0.94 meq / g, its viscosity was 402 poise / 30 ° C.,
The bromine number was 1 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.17.

Preparation Example 2 (1) Preparation of Liquid Polyisoprene Having a Hydroxyl Group at the Molecular Chain Terminal In a 1-liter stainless steel pressure-resistant reaction vessel, 200 g of isoprene, 100 g of a 30% hydrogen peroxide solution and 300 g of isopropanol were charged. The reaction was performed under the conditions of 115 ° C., a maximum pressure of 7 kg / cm ² , and a reaction time of 2.5 hours. After the reaction was completed, the reaction mixture was put into a separating funnel, 600 g of water was added thereto, and the mixture was shaken. After allowing to stand for 3 hours, the oil layer was separated. From this oil layer, solvent, monomer,
The low-boiling components were distilled off under the conditions of 2 mmHg, 100 ° C. and 2 hours to obtain a liquid polyisoprene having a hydroxyl group at a molecular chain terminal (yield: 71% by weight). This had a number average molecular weight of 1380, a hydroxyl group content of 1.55 meq / g, and a viscosity of 46 poise / 30 ° C. At this time, the average number of hydroxyl groups per molecule is 2.14. In addition, ¹ H-NMR
According to the results of structural analysis by
%, Cis-1,4 structure 33%, 1,2 structure 6%,
The 3,4 structure was 5%.

(2) Preparation of a hydride of liquid polyisoprene having a hydroxyl group at a molecular chain terminal 100 g of a liquid polyisoprene having a hydroxyl group at a molecular chain terminal obtained as described in (1) above and containing 5% by weight of ruthenium 5 g of a ruthenium carbon catalyst and 100 g of cyclohexane as a solvent were charged, and a hydrogenation reaction was carried out at 150 ° C. for 6 hours under a hydrogen pressure of 50 kg / cm ² G. After the completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter.
The solvent was distilled off under the condition of time. As a result, a hydride of liquid polyisoprene having a hydroxyl group at a molecular chain terminal was obtained. Its number average molecular weight was 1420, its hydroxyl group content was 1.54 meq / g, its viscosity was 298 poise / 30 ° C.,
The bromine number was 1 g / 100 g. At this time, the average number of hydroxyl groups per molecule is 2.19.

Preparation Example 3 (1) Preparation of Liquid Polyisoprene Having a Hydroxyl Group at a Molecular Chain Terminal
0 ml of n-hexane was charged and m-divinylbenzene 7.
15 g was added and dissolved. This is cooled to -10 ° C and n
48.0 ml of a 2.5 Mn-hexane solution of -butyllithium was added dropwise over 30 minutes. To this, 149.6 g of isoprene was added, and polymerized at 40 ° C. for 45 minutes. Then, the reaction was stopped by adding 176.4 g of ethylene oxide, and the obtained product was poured into 3 liters of methanol. The precipitate was treated under the conditions of 2 mmHg, 100 ° C. and 2 hours to obtain a liquid polyisoprene having a hydroxyl group in the molecule (96% by weight). This had a number average molecular weight of 3,120 and a hydroxyl group content of 0.61 meq / g. At this time, the average number of hydroxyl groups per molecule is 1.90.

(2) Preparation of a hydride of liquid polyisoprene having a hydroxyl group in the molecule 100 g of liquid polyisoprene having a hydroxyl group in the molecule obtained as described in (1) above, ruthenium carbon having a ruthenium content of 5% by weight 5 g of a catalyst and 100 g of cyclohexane as a solvent were charged, and 15 g under a hydrogen pressure of 50 kg / cm ² G.
The hydrogenation reaction was performed at 0 ° C. for 6 hours. After the reaction is completed, 0.
After the catalyst was separated and removed from the reaction solution through a 45 μm membrane filter, the solvent was distilled off under the conditions of 2 mmHg, 110 ° C. and 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group in the molecule was obtained. This had a number average molecular weight of 3210 and a hydroxyl group content of 0.3.
It was 58 meq / g. At this time, the average number of hydroxyl groups per molecule is 1.86.

Production Examples 1 to 11 (Preparation of Prepolymer) In a 3-liter separable flask equipped with an oil bath, a stirrer, a thermometer, and an Aline condenser, the polyisocyanate compound of the formulation shown in Table 1 was used. After removing the composition, a dehydration operation was carried out at 80 ° C. for 1 hour under reduced pressure of 2 mmHg with stirring. Thereafter, a polyisocyanate compound was added, and a reaction was carried out at 80 ° C. for 3 hours under a nitrogen stream to obtain a prepolymer. After the completion of the reaction, the temperature was lowered, sealed in a container sealed with nitrogen, and stored. Table 1 shows the isocyanate content of the obtained prepolymer.

[0066]

[Table 1]

[0067]

[Table 2]

[Footnotes to Table 1] * 1: Poly bd R-15HT, trade name, manufactured by Idemitsu Atchem Co., Ltd.
OH content = 1.82 meq / g * 2: Coronate T-, manufactured by Nippon Polyurethane Industry Co., Ltd.
100, NCO content = 48.3 wt% * 3: Daicel-Hüls K.K., NCO content = 37.
8 wt% * 4: Idemitsu Kosan Co., Ltd., liquid paraffin KP-8 * 5: Kyowa Hakko Co., Ltd., 2-ethyl-1,3-hexanediol, OH content = 13.68 meq / g * 6: obtained Phase separation was observed in the obtained prepolymer, and measurement was impossible. * 7: The entire system gelled during the reaction, and the prepolymer could not be obtained.

Examples 1 to 8 and Comparative Examples 1 to 3 Among the compositions shown in Table 2, the prepolymer was previously heated to 90 ° C.
The mixture was heated to 20 ° C., and these were combined and mixed and stirred for 2 minutes. This is a centrifugal molding machine (Toho Machinery Co., Ltd., E
S-300) and rotational molding was performed at 100 ° C. and 800 rpm for 1 hour to obtain a cured product having a thickness of 2 mm. This cured product was cured at 120 ° C. for 1 hour and further at 258 ° C. for 168 hours, and then subjected to a hot water resistance test, a chemical resistance test, a heat aging resistance test, and a weather resistance test as described below. The results are shown in Table 2.

1) Hot water resistance test The cured product was punched into a shape of 20 × 50 × 2 mm, and the weight change rate after immersion in distilled water at 70 ° C. for 336 hours was evaluated. The implementation of the test and the calculation of the rate of change were based on JIS K 6301, paragraph 12 (immersion test).

2) Chemical resistance test A cured product similar to the above was immersed in an alkaline aqueous solution prepared by dissolving Ca (OH) ₂ in distilled water to a pH of 11, and evaluated in the same manner as in the hot water resistance test. .

3) Heat aging resistance test A cured product similar to the above was punched out in the form of a No. 3 dumbbell specified in JIS K 6301, and the cured product was placed in a gear oven at 120 ° C. for 1 hour.
A 68-hour heat aging test was performed. The rate of change in tensile strength and elongation before and after the test was evaluated. JIS K
6301 Conforms to clause 12.

4) Weather Resistance Test An accelerated weather resistance test was performed under the following conditions.・ Testing machine model; WEL-6X-LHP (using WEL xenon lamp) manufactured by Suga Test Instruments Co., Ltd. ・ Black panel temperature: 60 ° C ・ Humidity: 60% RH ・ Irradiation time: 500 hours ・ Irradiation / (irradiation + rainfall) ) Cycle; 102min / 18min

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[Footnotes to Table 2] * 1: Poly (oxytetramethylene) glycol / tolylene diisocyanate prepolymer, product name: Adiprene L-100, manufactured by UNIROYAL Inc.
NCO content 4.1 wt%. * 2: manufactured by Ihara Chemical Co., Ltd., trade name: Iharacuamine MT, amine equivalent 7.49meq / g. * 3: Propylene oxide adduct of bisphenol A, manufactured by Japan Emulsifier Co., Ltd., OH content 5.03 meq / g. Number average molecular weight 400 * 4: A crack was generated on the sheet surface.

Example 9 The surface of a steel roll having a diameter of 40 mm and a length of 300 mm was coated with a composition having the same composition as in Example 2 so as to have a thickness of 2 mm. 120 ° C
And cured under the condition of 1 hour.
m). Two coated rolls are pressed at a pressure of 2 kgf.
Then, while pressing in parallel with each other, pressing the same lower part of the cross-section circle of both rolls in the same immersion liquid (with a temperature of 44 ° C.) as used in the chemical resistance test of Example 2 above. To 7 mm from the center (15 mm from the lower end of the arc)
After immersion, the two rolls were rotated inward at 200 rpm for 576 hours while keeping the two rolls in contact, and the coated surface was observed, but no change was observed.

Comparative Example 4 A test was conducted in the same manner as in Example 9 except that a roll coated with a composition having the same composition as that used in Comparative Example 2 was used. After the rotation, the coated surface showed swelling, tackiness, and whitening and devitrification.

[0080]

The polyurethane composition or the polyurethane-urea composition coated on the coating roll of the present invention is extremely excellent in (hot) water resistance and chemical resistance, and furthermore has heat aging resistance and weather resistance. Because of the excellent thermosetting polyurethane elastomer , the coated roll of the present invention also has these properties.
It is excellent. Therefore, the coating roll of the present invention
Suitable for rolls for steel, papermaking, office equipment, etc.
Can be used.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI D21F 3/08 D21F 3/08 F16C 13/00 F16C 13/00 AB (56) Reference JP-A-3-195720 (JP, A) JP-A-2-263821 (JP, A) JP-A-2-55748 (JP, A) JP-A-1-287113 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18 / 65,18 / 69 C09DD 175/04

Claims (1)

(57) [Claims] An average number of hydroxyl groups per molecule is 2.0 or more.
Hydrates of certain hydroxyl-containing liquid isoprene-based polymers
Reaction between (a) and the polyisocyanate compound (b)
And a polio having a molecular weight of 500 or less.
At least one selected from polyester compounds and polyamine compounds.
Polyurethane composition comprising one compound or poly
Coating of metal surface coated with urethane-urea composition
roll.